EP2315815A2 - Process for manufacture of packaging with grease barrier properties - Google Patents
Process for manufacture of packaging with grease barrier propertiesInfo
- Publication number
- EP2315815A2 EP2315815A2 EP09781801A EP09781801A EP2315815A2 EP 2315815 A2 EP2315815 A2 EP 2315815A2 EP 09781801 A EP09781801 A EP 09781801A EP 09781801 A EP09781801 A EP 09781801A EP 2315815 A2 EP2315815 A2 EP 2315815A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- polymers
- acid
- packaging
- anionic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 23
- 230000004888 barrier function Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000004519 grease Substances 0.000 title abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 92
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 54
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 42
- 229920006318 anionic polymer Polymers 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims description 54
- 229920001577 copolymer Polymers 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 33
- 239000000123 paper Substances 0.000 claims description 31
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 229920001519 homopolymer Polymers 0.000 claims description 20
- OSSNTDFYBPYIEC-UHFFFAOYSA-O 1-ethenylimidazole;hydron Chemical group C=CN1C=C[NH+]=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-O 0.000 claims description 18
- 239000008199 coating composition Substances 0.000 claims description 17
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 13
- 150000007513 acids Chemical class 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical group C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 8
- 239000005022 packaging material Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011111 cardboard Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 2
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000002985 plastic film Substances 0.000 claims 1
- 229920006255 plastic film Polymers 0.000 claims 1
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 36
- 125000000129 anionic group Chemical group 0.000 description 31
- 239000003925 fat Substances 0.000 description 17
- 125000002091 cationic group Chemical group 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000004971 Cross linker Substances 0.000 description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 12
- -1 allyl ethers Chemical class 0.000 description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 11
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000035515 penetration Effects 0.000 description 10
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 9
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 6
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 4
- 229940073608 benzyl chloride Drugs 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 4
- 229960003750 ethyl chloride Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011087 paperboard Substances 0.000 description 4
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- TYMYJUHDFROXOO-UHFFFAOYSA-N 1,3-bis(prop-2-enoxy)-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COCC=C TYMYJUHDFROXOO-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 229930006000 Sucrose Natural products 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- HMYBDZFSXBJDGL-UHFFFAOYSA-N 1,3-bis(ethenyl)imidazolidin-2-one Chemical compound C=CN1CCN(C=C)C1=O HMYBDZFSXBJDGL-UHFFFAOYSA-N 0.000 description 2
- RHBSVLZWJMBUBQ-UHFFFAOYSA-N 1-ethenyl-1h-imidazol-1-ium;chloride Chemical compound [Cl-].C=C[N+]=1C=CNC=1 RHBSVLZWJMBUBQ-UHFFFAOYSA-N 0.000 description 2
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 2
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- DCBBWYIVFRLKCD-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]-2-methylprop-2-enamide Chemical group CN(C)CCNC(=O)C(C)=C DCBBWYIVFRLKCD-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- NUTVORGGYDQIDD-UHFFFAOYSA-N 1-ethylsulfanylethanol Chemical compound CCSC(C)O NUTVORGGYDQIDD-UHFFFAOYSA-N 0.000 description 1
- LOXRGHGHQYWXJK-UHFFFAOYSA-N 1-octylsulfanyloctane Chemical compound CCCCCCCCSCCCCCCCC LOXRGHGHQYWXJK-UHFFFAOYSA-N 0.000 description 1
- GLGIHGJHHSONCV-UHFFFAOYSA-N 1-sulfanylpropane-1,2-diol Chemical compound CC(O)C(O)S GLGIHGJHHSONCV-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- PCUPXNDEQDWEMM-UHFFFAOYSA-N 3-(diethylamino)propyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C(C)=C PCUPXNDEQDWEMM-UHFFFAOYSA-N 0.000 description 1
- XUYDVDHTTIQNMB-UHFFFAOYSA-N 3-(diethylamino)propyl prop-2-enoate Chemical compound CCN(CC)CCCOC(=O)C=C XUYDVDHTTIQNMB-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 description 1
- WZISPVCKWGNITO-UHFFFAOYSA-N 4-(diethylamino)-2-methylidenebutanamide Chemical compound CCN(CC)CCC(=C)C(N)=O WZISPVCKWGNITO-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical compound OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 description 1
- HDWNKEWYEDOKIZ-UHFFFAOYSA-N 5-(diethylamino)-2-methylidenepentanamide Chemical compound CCN(CC)CCCC(=C)C(N)=O HDWNKEWYEDOKIZ-UHFFFAOYSA-N 0.000 description 1
- LVGSUQNJVOIUIW-UHFFFAOYSA-N 5-(dimethylamino)-2-methylpent-2-enamide Chemical compound CN(C)CCC=C(C)C(N)=O LVGSUQNJVOIUIW-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229920001448 anionic polyelectrolyte Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RRPJQNOJVXGCKC-UHFFFAOYSA-M methyl-tris(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(CC=C)CC=C RRPJQNOJVXGCKC-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31779—Next to cellulosic
- Y10T428/31783—Paper or wood
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
Definitions
- the invention relates to a process for producing packaging, wherein the packaging surface is coated with a polyelectrolyte complex and wherein the polyelectrolyte complex consists of at least a first polymer and at least one second polymer, wherein the first polymer is an anionic polymer and the second polymer is a cationic polymer.
- the packaging is characterized by good fat barrier properties.
- the packaging materials used When packaging oily or fatty products, it is important that the packaging materials used have a high penetration resistance to fats and oils or good fat barrier properties.
- Various methods are known which are suitable for imparting a penetration resistance to fats and oils to packaging materials, in particular based on paper or cardboard.
- the materials can be impregnated or coated, for example, with solutions or aqueous dispersions of native or synthetic polymers, paraffins, waxes or fluorinated hydrocarbons. These are e.g. solutions of starches and starch derivatives, galactomannans, carboxymethylcelluloses, polyvinyl alcohols or solutions of other synthetic polymers, for example anionic polyacrylamides.
- a paper produced by such a method has only a low density of fat.
- EP 1498544 discloses coatings based on polymer emulsions for cellulosic substrates having barrier properties.
- the polymers are ethylene-vinyl acetate copolymers (EVA).
- EVA ethylene-vinyl acetate copolymers
- From US 2007092718 a method is known for improving the fat and / or water resistance of materials, wherein the material is treated with wax and polyvinyl alcohol.
- DE 10 2005 007 483 aqueous dispersions of predominantly anionically charged polyelectrolyte complexes are known.
- fat barrier coatings are not sufficiently flexible with polymer based films. It may then crease or fold in the area of folds, e.g. Edges or corners of cartons or cartons will damage the barrier film resulting in insufficient fat barrier effects.
- the object of the present invention was to provide a process which allows the production of packagings with good grease and oil barrier properties. shadow, especially in the area of folds, creases and corners allows.
- the packaging should be as good as possible temperature resistant, flexible and block-resistant and as possible no harmful substances such as heavy metals and possibly contain no fluorocarbon compounds.
- the invention relates to a method for producing a packaging, wherein at least a part of the packaging surface is coated with at least one polyelectrolyte complex, wherein the polyelectrolyte complex consists of at least a first polymer and at least one second polymer, wherein the first polymer is an anionic polymer and the second polymer is a cationic polymer.
- the invention also provides a packaging made from a packaging material whose surface is at least partially coated with a polyelectrolyte complex, wherein the polyelectrolyte complex consists of at least a first polymer and at least one second polymer, wherein the first polymer is an anionic polymer and the second polymer cationic polymer.
- the invention also provides the use of polyelectrolyte complexes for the production of coated packaging, wherein at least part of the surface of the packaging is coated with at least one polyelectrolyte complex, wherein the polyelectrolyte complex consists of at least one first polymer and at least one second polymer, wherein the first Polymer is an anionic polymer and the second polymer is a cationic polymer.
- the coating made with the polyelectrolyte complex preferably has fat barrier properties.
- the barrier properties can be measured with the penetration test described in the examples.
- the term fat barrier property means an increased resistance of a substrate surface to the penetration of fats, oils and fatty and oil-like, hydrophobic substances compared to uncoated substrate.
- Polyelectrolytes are ionic polymers.
- Polyelectrolyte complexes are the reaction products of oppositely charged ionic polymers.
- the polyelectrolyte complexes have a defined stoichiometric composition, ie the equivalent ratio of anionic and cationic groups in these complexes is at or in the vicinity of 1.
- the polyelectrolyte complexes can also be predominantly anionic or predominantly cationically charged.
- a cationic or an anionic polymer may additionally be present in excess, ie in free, uncomplexed form.
- aqueous dispersions of polyelectrolyte complexes Preference is given to using aqueous dispersions of polyelectrolyte complexes.
- the polyelectrolyte complexes are preferably predominantly anionically charged.
- the dispersions can be obtained by free-radical polymerization of ethylenically unsaturated anionic monomers in an aqueous medium in the presence of at least one cationic polymer; in one embodiment, the anionic monomers are used in an amount such that the number of anionic groups in the anionic monomers is the number of the cationic groups in the cationic polymers exceeds at least 1 mol%, measured at pH 7 and 20 ° C.
- a suitable preparation process is described, for example, in DE 10 2005 007 483.
- the amount of cationic polymer which is used to prepare the polyelectrolyte complex is preferably such that, for example, up to 150 mol% or up to 100 mol per mol of the anionic groups of the anionic polymer or in the anionic monomers used in total during the polymerization mol%, preferably 1 to 99 mol% or 2 to 50 mol% of cationic groups of at least one cationic polymer, measured at pH 7 and 20 0 C.
- the polyelectrolyte complexes formed with less than 100 mol% of cationic groups are at pH 7 and 20 ° C predominantly anionic charged.
- Anionic polymers are polymers with anionic groups, in particular organic polymers with carboxylate, phosphate or sulfate groups. It is also possible to use the corresponding acids, provided that they are either neutralized by bases present in the reaction medium or converted into anionic groups by basic groups of the cationic polymer.
- Suitable anionic polymers are e.g. those formed by radical polymerization of ethylenically unsaturated, radically polymerizable anionic polymers. This also includes copolymers of at least one anionic monomer and one or more different nonionic copolymerizable monomers.
- Suitable ethylenically unsaturated anionic monomers are monoethylenically unsaturated C.sub.3- to C.sub.10- or C.sub.3- to C.sub.-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, itaconic acid and the alkali metal, alkaline earth metal or ammonium salts of these acids into consideration.
- monoethylenically unsaturated anionic monomers are monoethylenically unsaturated C.sub.3- to C.sub.10- or C.sub.3- to C.sub.-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylsulf
- Preferred anionic monomers include acrylic acid, methacrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid. Particularly preferred are aqueous dispersions of polymers based on acrylic acid.
- the anionic monomers can be polymerized either alone to form homopolymers or else mixed with one another to give copolymers. Examples of these are the homopolymers of acrylic acid, homopolymers of methacrylic acid or copolymers of acrylic acid and maleic acid, copolymers of acrylic acid and methacrylic acid and copolymers of methacrylic acid and maleic acid.
- the polymerization of the anionic monomers can also be carried out in the presence of at least one other ethylenically unsaturated monomer.
- These monomers may be nonionic or may carry a cationic charge.
- nonionic comonomers are acrylamide, methacrylamide, N-Cr to C3-alkylacrylamides, N-vinylformamide, acrylic esters of monohydric alcohols having 1 to 20 C atoms, in particular methyl acrylate, ethyl acrylate, isobutyl acrylate and n-butyl acrylate, methacrylic acid esters of monohydric alcohols with 1 up to 20 C-atoms eg Methyl methacrylate and ethyl methacrylate, as well as vinyl acetate and vinyl propionate.
- Suitable cationic monomers which can be copolymerized with the anionic monomers are dialkylaminoethyl acrylates, dialkylaminoethyl methacrylates, dialkylaminopropyl acrylates, dialkylaminopropyl methacrylates, dialkylaminoethylacrylamides, dialkylaminoethylmethacrylamides, dialkylaminopropylacrylamides, dialkylaminopropylmethacrylamides, diallyldimethylammonium chloride, vinylimidazole and also the basic monomers neutralized and / or quenched with acids , Specific examples of cationic monomers are dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate,
- the basic monomers may be completely or even partially neutralized or quaternized, for example, in each case from 1 to 99%.
- Preferred quaternizing agent for the basic monomers is dimethylsulfate.
- the quaternization of the monomers can also be carried out with diethyl sulfate or with alkyl halides such as methyl chloride, ethyl chloride or benzyl chloride.
- the cationic monomers are used most in an amount such that the resulting polyelectrolyte lytkomplexe total at pH values ⁇ 6.0 and carry a temperature of 20 C 0 an anionic charge.
- the anionic excess charge in the resulting amphoteric polymers is, for example, at least 5 mol%, preferably at least 10 mol%.
- the comonomers are used in the preparation of the anionic polyelectrolyte complexes, for example in amounts such that the resulting polymer dispersions when diluted with water and at pH values above 7.0 and a temperature of 20 0 C are water-soluble and have an anionic charge.
- the Amount of nonionic and / or cationic comonomers for example 0 to 99, preferably 5 to 75 wt .-% and is usually in the range of 5 to 25 wt .-%.
- Examples of preferred copolymers are copolymers of 25 to 90% by weight of acrylic acid and 75 to 10% by weight of acrylamide.
- Particular preference is given to homopolymers of acrylic acid obtainable by free-radical polymerization of acrylic acid in the absence of other monomers.
- the anionic polymer contains 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
- AMPS 2-acrylamido-2-methylpropanesulfonic acid
- acrylic acid is copolymerized with AMPS.
- the amount of AMPS can be, for example, from 0.1 to 15 mol% or from 0.5 to 10 mol%, based on the amount of all monomers.
- the polymerization can additionally be carried out in the presence of at least one crosslinker. Copolymers having a higher molecular weight are then obtained than when the anionic monomers are polymerized in the absence of a crosslinking agent.
- the incorporation of a crosslinker in the polymers also leads to a reduced solubility of the polymers in water. Depending on the amount of copolymerized crosslinker, the polymers become water-insoluble, but are swellable in water.
- Crosslinkers which can be used are all compounds which have at least two ethylenically unsaturated double bonds in the molecule.
- crosslinkers are triallylamine, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, methylenebisacrylamide, N, N'-divinylethyleneurea, allyl ethers containing at least two allyl groups or vinyl ethers of polyhydric alcohols having at least two vinyl groups, for example sorbitol, 1,2-ethanediol, 1,4-butanediol , Trimethylolpropane, glycerol, diethylene glycol and of sugars such as sucrose, glucose, mannose, completely esterified with acrylic or methacrylic dihydric alcohols having 2 to 4 carbon atoms such as ethylene glycol dimethacrylate, ethylene glycol diol, Butandioldimethacrylat, Butandioldiacrylat, diacrylates or dimethacrylates of polyethylene glycols having molecular weights of 300 to 600, ethoxylated trimethyleneprop
- crosslinking agents are used in the preparation of the dispersions of the invention, the amounts of crosslinker used in each case are, for example, from 0.0005 to 5.0, preferably from 0.001 to 1, 0% by weight, based on the total monomers used in the polymerization.
- Preferred crosslinkers are pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, N, N'-divinylethyleneurea, control for at least two allyl groups-containing allyl ethers of sugars such as sucrose, glucose or mannose, and triallylamine and mixtures of these compounds.
- the polymerization of at least one anionic monomer is carried out in the presence of at least one crosslinking agent, it is preferable to prepare crosslinked copolymers of acrylic acid and / or methacrylic acid by reacting acrylic acid and / or methacrylic acid in the presence of pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, N, N '.
- Divinylethyleneurea at least two allyl-containing allyl ethers of sugars such as sucrose, glucose or mannose or triallylamine and mixtures of these compounds polymerized.
- the resulting polyelectrolyte complexes are soluble or swellable in dilute aqueous solution at pH values> 7.0.
- the cationic polymers used for forming the polyelectrolyte complexes are preferably water soluble, meaning they have a solubility in water of at least 1 g / l at 20 0 C.
- Cationic polymers are polymers with cationic groups, in particular organic polymers with quaternary ammonium groups. It is also possible to use polymers having primary, secondary or tertiary amine groups, provided that they are either protonated by acids contained in the reaction medium or by acid groups of the anionic polymer and thus converted into cationic groups.
- the amine or ammonium groups of the cationic polymer can be present as substituents or as part of the polymer chain. They may also be part of an aromatic or non-aromatic ring system.
- Suitable cationic polymers are e.g. Polymers from the group of
- polydimethylaminoethyl acrylate polydimethylaminoethyl methacrylate, copolymers of acrylamide and dimethylaminoethyl acrylate and copolymers of acrylamide and dimethylaminoethyl methacrylate, where the basic monomers may also be present in the form of the salts with mineral acids or in quaternized form
- polydimethylaminoethylacrylamide, polydimethylaminoethylmethacrylamide and copolymers of acrylamide and dimethylaminoethylacrylamide polydimethylaminoethylacrylate, polydimethylaminoethyl methacrylate, copolymers of acrylamide and dimethylaminoethylacrylamide.
- the basic monomers can also be present in the form of the salts with mineral acids or in quaternized form.
- the average molecular weights M w of the cationic polymers are at least 500. They are for example in the range of 500 to 1 million, preferably from 1,000 to 500,000 or 2,000 to 100,000.
- cationic polymers are (a) homopolymers of vinylimidazolium methosulfate and / or copolymers of vinylimidazolium methosulfate and N-vinylpyrrolidone having an average molecular weight Mw of from 500 to 500,000, (b) polydiallyldimethylammonium chlorides having an average molecular weight M w of from 1000 to 500,000, (c) polyvinylamines having an average molecular weight M w of 500 to 1 million; and (d) polyethyleneimines having an average molecular weight M w of 500 to 1 million.
- the copolymers of vinylimidazolium methosulfate and N-vinylpyrrolidone listed under (a) contain, for example, 10 to 90% by weight of N-vinylpyrrolidone polymerized.
- N-vinylpyrrolidone can be used as comonomer at least one compound from the group of ethylenically unsaturated C3 to Cs carboxylic acids such as acrylic acid or methacrylic acid or esters of these carboxylic acids with 1 to 18 carbon atoms containing monohydric alcohols such as methyl acrylate, ethyl acrylate , Isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate or n-butyl methacrylate.
- Polymers of group (b) are preferably polydiallyldimethylammonium chloride. Also suitable are copolymers of diallyldimethylammonium chloride and dimethylaminoethyl acrylate, copolymers of diallyldimethylammonium chloride and dimethylaminoethyl methacrylate, copolymers of diallyldimethylammonium chloride and diethylaminoethyl acrylate, copolymers of diallyldimethylammonium chloride and dimethylaminopropyl acrylate, copolymers of dialkyldimethylammonium chloride and dimethylaminoethylacrylamide and copolymers of diallyldimethylammonium chloride and dimethylaminopropylacrylamide.
- the copolymers of diallyldimethylammonium chloride contain, for example, from 1 to 50, usually from 2 to 30, mol% of at least one of the abovementioned com
- Vinylamine-containing polymers (c) are obtainable by polymerizing N-vinylformamide optionally in the presence of comonomers and hydrolysing the vinylformamide polymers with elimination of formyl groups to form amino groups.
- the degree of hydrolysis of the polymers may be, for example, 1 to 100%, and most often in the range of 60 to 100%.
- the average molecular weights M w amount up to 1 million.
- Vinylamine-containing polymers are sold, for example as Catiofast® ® trademarks of BASF SE.
- Ethylenimine units containing polymers of group (d) such as polyethyleneimines are also commercial products. They are, for example, under the name poly min® of BASF SE sold eg Polymin® ® SK. These cationic polymers are polymers of ethyleneimine which are prepared by polymerizing ethyleneimine in an aqueous medium in the presence of small amounts of acids or acid-forming compounds such as halogenated hydrocarbons such as chloroform, carbon tetrachloride, tetrachloroethane or ethyl chloride or condensation products of epichlorohydrin and amino groups containing compounds such as mono- and polyamines such as dimethylamine, diethylamine, ethylenediamine, diethylenetriamine and triethylenetetramine or ammonia. They have, for example, molar masses M w of 500 to 1 million, preferably 1000 to 500,000.
- This group of cationic polymers also includes graft polymers of ethyleneimine on compounds having a primary or secondary amino group, e.g. Polyamidoamines from dicarboxylic acids and polyamines. If desired, the polyamidoamines grafted with ethyleneimine can also be reacted with bifunctional crosslinkers, for example with epichlorohydrin or bis-chlorohydrin ethers of polyalkylene glycols.
- Suitable cationic polymers of group (e) are polymers containing dialkylaminoalkyl acrylate and / or dialkylaminoalkyl methacrylate units. These monomers can be used in the form of the free bases, but preferably in the form of the salts with mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid and in quaternized form in the polymerization. Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride, cetyl chloride or benzyl chloride. From these monomers, both homopolymeric and copolymers can be prepared.
- Suitable comonomers are, for example, acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, methyl methacrylate and mixtures of the stated monomers.
- Cationic polymers of group (f) are dimethylaminoethylacrylamide or dimethylaminoethyl methacrylamide units containing polymers which contain the basic monomers preferably in the form of salts with mineral acids or in quaternized form. These may be homopolymers and copolymers.
- Examples are homopolymers of dimethylaminoethylacrylamide which is completely quaternized with dimethyl sulphate or with benzyl chloride, homopolymers of dimethylaminoethyl methacrylamide which is completely quaternized with dimethyl sulphate, methyl chloride, ethyl chloride or benzyl chloride, and also copolymers of acrylamide and dimethylaminoethyl acrylamide quaternized with dimethyl sulphate.
- the following cationic polymers are preferably used:
- the polyvinylamines are preferably used in the form of salts with sulfuric acid or hydrochloric acid.
- amphoteric polymers as cationic polymers, provided that they carry a total cationic charge.
- the kationi see excess charge in the amphoteric polymers, for example, at least 5 mol%, preferably at least 10 mol% and is usually in the range of 15 to 95 mol%.
- amphoteric polymers with a cationic excess charge are examples of amphoteric polymers with a cationic excess charge.
- Copolymers of acrylamide, dimethylaminoethyl acrylate and acrylic acid which contain at least 5 mol% more dimethylaminoethyl acrylate as copolymerized with acrylic acid;
- Copolymers of vinylimidazolium methosulfate, N-vinylpyrrolidone and acrylic acid which contain at least 5 mol% more vinylimidazolium methosulfate copolymerized as acrylic acid; hydrolyzed copolymers of N-vinylformamide and an ethylenically unsaturated C 3 -C 6 -carboxylic acid, preferably acrylic acid or methacrylic acid, with at least 5 mol% higher vinylamine units than units of ethylenically unsaturated carboxylic acids;
- Copolymers of vinylimidazole, acrylamide and acrylic acid wherein the pH is selected so that at least 5 mol% more vinylimidazole is cationically charged when acrylic acid is copolymerized.
- Aqueous dispersions of polyelectrolyte complexes can be prepared by free-radically polymerizing the anionic monomers in question, if appropriate in the presence of other monomers, in an aqueous medium in the presence of cationic polymers.
- the amount of basic or cationic monomers can be chosen such that the resulting polymer complexes always carry an excess of anionic charge, determined at pH 7 and 20 ° C.
- the determination of the charge density of the polyelectrolytes or polyelectrolyte complexes can be carried out according to D. Hörn, Progr. Colloid & Polymer Sci., Vol. 65, 251-264 (1978).
- Basic polymers are preferably used in the form of the salts with mineral acids or organic acids such as formic acid or acetic acid in the polymerization. Otherwise, these salts form anyway in the polymerization, because the polymerization is carried out at a pH ⁇ 6.0.
- aqueous dispersions of predominantly anionically charged polyelectrolyte complexes which are preferred according to the invention can be prepared by free-radical polymerization of ethylenically unsaturated anionic monomers in aqueous medium in the presence of at least one water-soluble cationic polymer, preferably 0.5 g per mole of the anionic monomers used in the polymerization to 49 mol% of at least one cationic polymer.
- the polymerization is carried out in aqueous medium at a pH below 6, e.g. in the range of 0 to 5.9, preferably 1 to 5 and in particular of 1, 5 to 3.
- the pH in question is usually obtained by adding acid group-containing polymers in the form of free acid groups in the polymerization starts.
- the pH can be varied by adding a base such as in particular aqueous sodium hydroxide solution or potassium hydroxide solution for partial neutralization of the acid groups of the anionic monomers in the specified range.
- a base such as in particular aqueous sodium hydroxide solution or potassium hydroxide solution for partial neutralization of the acid groups of the anionic monomers in the specified range.
- a base such as in particular aqueous sodium hydroxide solution or potassium hydroxide solution for partial neutralization of the acid groups of the anionic monomers in the specified range.
- a base such as in particular aqueous sodium hydroxide solution or potassium hydroxide solution for partial neutralization of the acid groups of the anionic monomers in the specified range.
- alkali metal, alkaline earth metal or ammonium salts of anionic monomers is added either a mineral acid or an organic acid such as formic acid, acetic acid or propionic acid to adjust the pH.
- the polymerization can additionally be carried out in the presence of at least one chain transfer agent.
- chain transfer agents are organic compounds which contain sulfur in bonded form, such as dodecylmercaptan, thiodiglycol, ethylthioethanol, di-n-butylsulfide, di-n-octylsulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, Mercaptopropan-1, 2-diol, 1, 4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptobernic acid, thioacetic acid and thiourea, aldehydes, organic acids such as formic acid, sodium formate or ammonium formate, alcohols such as isopropanol and phosphorus compounds,
- the chain transfer agents are preferably used together with at least one crosslinker in the polymerization. By varying the amount and the ratio of chain transfer agent and crosslinker, it is possible to control the rheology of the resulting polymers.
- Chain carriers and / or crosslinkers can be initially introduced during the polymerization, for example in the aqueous polymerization medium, or dosed together or separately from the monomers, depending on the progress of the polymerization, to the polymerization batch.
- the polymerization usually uses initiators which form radicals under the reaction conditions.
- Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, sodium or potassium persulfate, redox catalysts and azo compounds such as 2,2-azobis (N, N-dimethyleneisobutyricin) dihydrochloride, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile ), 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride.
- the initiators are used in the amounts customary in the polymerization.
- Azo starters are preferably used as polymerization initiators.
- the polymerization can also be initiated by means of high-energy radiation such as electron beams or by irradiation with UV light.
- the polymerization of the anionic monomers is carried out, for example, batchwise by initially introducing the monomers and at least one cationic compound in a polymerization zone and metering the polymerization initiator in portions or continuously.
- the polymerization is usually carried out in all cases with the exclusion of oxygen under an inert gas atmosphere, for example under nitrogen or helium.
- the polymerization temperatures are for example in the range of 5 to 100 0 C, preferably 15 to 90 0 C and usually at 20 to 70 0 C. The polymerization temperature depends very much on the particular initiator which is used.
- the concentration of the polyelectrolyte complexes in the solutions or aqueous dispersions used for the coating is preferably at least 1% by weight, in particular at least 5% by weight and up to 50 or up to 60% by weight. In most cases, the content of polyelectrolyte complexes in the aqueous dispersion is from 1 to 40% by weight or from 5 to 35% by weight, in particular from 15 to 30% by weight.
- Preferred aqueous dispersions of polyelectrolyte complexes have at pH values below 6.0 and a temperature of 20 0 C a viscosity from 100 to 150,000 mPas, or from 200 to 5000 mPas (measured with a Brookfield viscometer at 20 0 C, 20 Rpm, spindle 4).
- the polyelectrolyte complexes have different molecular weights.
- the average molecular weight M w of the polyelectrolyte complexes is, for example, 1,000 to 10 million, preferably 5,000 to 5 million, and is usually in the range of 10,000 to 3 million.
- the molecular weight is determined with the aid of light scattering.
- the average particle size of the dispersed polyelectrolyte complexes is, for example, 0.1 to 200 ⁇ m, preferably 0.5 to 70 ⁇ m. You can z. B. with the help of optical microscopy, light scattering or freeze-fracture electron microscopy are determined.
- suitable substrates for packaging are coated with an aqueous solution or dispersion of at least one polyelectrolyte complex.
- Suitable substrates are in particular paper, board and foils, e.g. made of plastic or metal.
- the solutions or dispersions used for the coating may contain further additives or auxiliaries, e.g. Thickener for adjusting the rheology, wetting aids or binders.
- the application can be carried out, for example, on coating machines in such a way that the coating composition is applied to paper, cardboard or to a carrier foil made of a plastic or a metal. If web-shaped materials are used, the polymer dispersion is usually applied from a trough over an applicator roll and leveled with the aid of an air brush. Other ways of applying the coating succeed, for example. using the reverse gravure method, by spraying or with a roller blade.
- the polyelectrolyte complex is first formed in situ on the packaging material by applying two coating compositions simultaneously or in one step immediately after one another, for example by a cascade coating, wherein one of the coating compositions contains at least one anionic polymer and the other coating composition contains at least one cationic polymer. It is preferred that initially at least one first coating composition is applied, which contains at least one cationic polymer having primary, secondary or tertiary amine groups and then at least one second coating composition is applied, which contains at least one anionic polymer having acid groups.
- the cationic polymers having amino groups are, for example, polymers having units selected from the group consisting of vinylamine, ethyleneimine, dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, dialkylaminoalkylacrylamide, dialkylaminoalkylmethacrylamide and mixtures thereof; in particular polyvinylamines, polyethylenimines, polydimethylaminoethyl acrylate, polydimethylaminoethyl methacrylate, copolymers of acrylamide and dimethylaminoethyl acrylate and copolymers of acrylamide and dimethylaminoethyl methacrylate.
- the anionic polymers having acid groups are, for example, polymers having units selected from acrylic acid, methacrylic acid, maleic acid, 2-acrylamido-2-methylpropanesulfonic acid and mixtures thereof, in particular homopolymers of acrylic acid and copolymers of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
- the carrier film may be previously subjected to a corona treatment.
- the amounts applied to the sheet-like materials are, for example, preferably 1 to 10 g (polymer, solids) per m 2 , preferably 2 to 7 g / m 2 for films, or preferably 10 to 30 g / m 2 for paper or cardboard ,
- the solvent is evaporated.
- the material may pass through a dryer channel which may be equipped with an infrared radiation device. Thereafter, the coated and dried material is passed over a cooling roll and finally wound up.
- the thickness of the dried coating is preferably 1 to 50 ⁇ m, more preferably 2 to 20 ⁇ m.
- the substrates coated with the polyelectrolyte complex show an excellent barrier action against fats and oils, in particular in the area of kinks, folds and corners of packaging made of paper or cardboard.
- the coated substrates can be used as such as packaging, preferably for food.
- the coatings have very good mechanical properties, and show e.g. Good block behavior and show essentially no cracking.
- the coated ones Overcoat substrates with topcoats which additionally impart these desired properties.
- the substrates precoated with polyelectrolyte complexes show good overcoatability. It can be overcoated again according to a method mentioned above or coated several times in a continuous process without intermediate winding and unwinding, for example of the film or of the paper.
- the fat barrier layer is thereby inside the system, the surface properties are then determined by the cover layer.
- the cover layer has good adhesion to the fat barrier layer.
- fat and oil impermeable coatings e.g. on films of oriented polypropylene or polyethylene, wherein the polyethylene may have been prepared both by high pressure and by the low pressure polymerization process of ethylene.
- suitable carrier films are, for example, films of polyester, such as polyethylene terephthalate, films of polyamide, polystyrene and polyvinyl chloride.
- Suitable support materials are also papers and metal foils such as aluminum foil.
- the thickness of the carrier films is generally in the range of 10 to 200 microns, in films of polyamide at 30 to 50 microns, in films of polyethylene terephthalate at 10 to 40 microns, in films of polyvinyl chloride at about 200 microns and films of polystyrene at about 20 microns.
- support materials made of paper or paperboard are particularly preferred.
- Coated paper The polyelectrolyte complex dispersions are used without further purification to coat paper.
- the paper used has a basis weight of 60-80 g / m 2 .
- the paper is precoated with a pigmented coating color to form a thin polymer coating (0.5 ⁇ m) for pore balance. With a roller blade, the pre-coated papers are coated with one of the dispersions 1 to 5 in a layer thickness between 15 and 20 microns (after drying).
- a first coating composition contains 6% by weight of polyvinylamine in water.
- a second coating composition contains 20% by weight of polyacrylic acid in water.
- the above paper is coated first with 3.5 g / m 2 of the first coating composition and then with 12 g / m 2 of the second coating composition.
- Comparative Example C1 Coating with Cationic Polymer The abovementioned paper is coated with 10 g / m 2 of a coating composition which contains as the sole polymer 20% by weight of a 5% hydrolysed poly (N-vinylformamide) in water.
- the above paper is coated as above with a coating composition containing as the sole polymer 20% by weight of polyacrylic acid in water.
- the layer thickness of the coating was 20 ⁇ m and the basis weight was 20 g / m 2 (dry).
- the films are flexible and stable (at least) up to 80 ° C.
- the coatings are resistant to blocking at 80 0 C. After heating to 80 ° C. for 72 hours under a pressure of 100 N / m 2, there is no degeneration or stickiness.
- test solutions T1 to T12 are used:
- test series with unfolded, smooth paper and one test series with folded paper are carried out.
- the coated paper is folded up and unfolded again.
- the test solutions are added dropwise to the fold resulting from the folding. In each case the highest number of the test solution is noted, in which no staining was observed. The final value is the mean of 5 examinations, rounded to 0.5.
- test substances were used: a) oleic acid b) mixture of 900 g of turpentine, and 100 g mineral oil having a boiling point 100-140 0 C and 2.5 g of Sudan Blue
- test substance is applied to the coated paper side.
- test substance b because of the volatility of the substance, the application of the substance was repeated from time to time to ensure permanent wetting. After the periods indicated in the table below, the percentage of blue-colored fatty sites on the uncoated paper surface is determined. The values given correspond to the approximate percentage of blue-colored surface. Table 3 Penetration test with oleic acid
Abstract
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JP5882209B2 (en) * | 2009-08-24 | 2016-03-09 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Use of polyelectrolyte composites for the production of polymer sheets with oxygen barrier properties |
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WO2011095444A1 (en) | 2010-02-03 | 2011-08-11 | Basf Se | Associative thickening agent made of acid monomers, associative monomers, and non-ionic monomers |
US8637160B2 (en) | 2010-06-14 | 2014-01-28 | Basf Se | Polymer dispersions of vinylaromatic compounds and acrylate monomers prepared in the presence of seed latex and carbohydrate compounds |
-
2009
- 2009-08-13 US US13/057,919 patent/US8747955B2/en not_active Expired - Fee Related
- 2009-08-13 PT PT09781801T patent/PT2315815E/en unknown
- 2009-08-13 CN CN200980132675.9A patent/CN102131877B/en not_active Expired - Fee Related
- 2009-08-13 EP EP20090781801 patent/EP2315815B1/en active Active
- 2009-08-13 WO PCT/EP2009/060495 patent/WO2010020581A2/en active Application Filing
- 2009-08-13 CA CA2733755A patent/CA2733755C/en not_active Expired - Fee Related
- 2009-08-13 PL PL09781801T patent/PL2315815T3/en unknown
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DE102015210395A1 (en) | 2015-06-05 | 2016-12-08 | Technische Universität Dresden | Filter device and a method for the selective separation of an analyte from a liquid |
Also Published As
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WO2010020581A3 (en) | 2010-07-01 |
US8747955B2 (en) | 2014-06-10 |
CN102131877A (en) | 2011-07-20 |
CA2733755C (en) | 2016-10-11 |
CA2733755A1 (en) | 2010-02-25 |
EP2315815B1 (en) | 2014-01-08 |
CN102131877B (en) | 2015-04-15 |
US20110143156A1 (en) | 2011-06-16 |
WO2010020581A2 (en) | 2010-02-25 |
PT2315815E (en) | 2014-03-06 |
PL2315815T3 (en) | 2014-06-30 |
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